WO2012060208A1 - Procédé de production de microparticules de métal - Google Patents

Procédé de production de microparticules de métal Download PDF

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Publication number
WO2012060208A1
WO2012060208A1 PCT/JP2011/073877 JP2011073877W WO2012060208A1 WO 2012060208 A1 WO2012060208 A1 WO 2012060208A1 JP 2011073877 W JP2011073877 W JP 2011073877W WO 2012060208 A1 WO2012060208 A1 WO 2012060208A1
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Prior art keywords
electrolytic bath
metal
oxide powder
metal oxide
molten salt
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PCT/JP2011/073877
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English (en)
Japanese (ja)
Inventor
伊藤　靖彦
学 徳重
錦織　徳二郎
浩行 辻村
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学校法人同志社
アイ’エムセップ株式会社
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Priority to JP2012541802A priority Critical patent/JPWO2012060208A1/ja
Priority to US13/882,816 priority patent/US9562296B2/en
Publication of WO2012060208A1 publication Critical patent/WO2012060208A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
    • C25C5/04—Electrolytic production, recovery or refining of metal powders or porous metal masses from melts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • C01B33/021—Preparation
    • C01B33/023—Preparation by reduction of silica or free silica-containing material
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Definitions

  • the present invention generally relates to a method for producing metal fine particles, and specifically relates to a method for producing metal fine particles by molten salt electrolysis.
  • metal fine particles for example, there is a plasma induced electrolysis method using cathode discharge.
  • metal fine particles can be formed in the molten salt by electrochemically reducing metal ions in the molten salt with discharge electrons generated from the cathode.
  • Patent Document 1 International Publication No. 2005/111272 (Patent Document 1) describes a method for producing metal fine particles by a plasma-induced electrolysis method, and melts a raw material containing an oxide of a metal constituting the target metal fine particles. It is described that metal ions are supplied in molten salt by dissolving in salt. In addition, it is described that an anode containing a metal constituting a target metal fine particle is disposed in a molten salt, and metal ions are supplied into the molten salt by electrochemical dissolution from the anode.
  • Non-patent Document 1 describes a method for producing silver fine particles by plasma-induced electrolysis.
  • a method is used in which silver chloride is used as a raw material as a halide containing silver, and is added to a molten salt and chemically dissolved to generate silver ions.
  • Patent Document 2 discloses a metal in contact with the surface of a cathode immersed in an electrolytic bath by suspending a metal oxide powder in a molten salt to form an electrolytic bath. A method is described in which oxide powder is electrochemically reduced and deposited on the cathode.
  • Non-Patent Document 1 a metal halide is used as a compound that can be dissolved in a molten salt. Therefore, it is necessary to separately prepare a metal halide constituting the target metal fine particles.
  • a metal oxide powder which is generally easily available at a low cost in the market, as a raw material, in order to chemically dissolve the raw material in the molten salt, The composition of the molten salt is greatly limited.
  • the raw material used as the anode needs to contain the metal constituting the target metal fine particles, and only the metal oxide powder is used as the anode. Thus, it is difficult to supply metal ions into the molten salt.
  • the metal oxide powder in the electrolytic bath is electrochemically reduced on the cathode surface disposed in the electrolytic bath, and the target metal is in the form of a film. Electrodeposit on. Therefore, it is difficult to recover the metal electrodeposited in the form of a film.
  • the component of the cathode base material may be mixed as an impurity in the deposited metal.
  • an object of the present invention is to provide a method for producing metal fine particles, in which metal oxide powder can be used as a raw material, and impurities are not easily mixed in the electrolytic bath and the produced metal fine particles. is there.
  • a metal oxide powder is used as a raw material, suspended in a molten salt to form an electrolytic bath, and plasma-induced electrolysis is performed on the electrolytic bath. Reduce chemically.
  • the method for producing fine metal particles according to the present invention reduces the metal oxide powder in the electrolytic bath by generating a cathode discharge in the vicinity of the surface of the electrolytic bath in which the metal oxide powder is suspended in the molten salt. .
  • the metal oxide powder is generally easily available. Further, since the metal oxide powder may be suspended in the molten salt, there is a limitation imposed on the composition of the molten salt used compared to the case where the metal oxide is chemically dissolved in the molten salt. Alleviated.
  • the metal is deposited on the cathode by reducing the metal oxide powder with discharge electrons in the vicinity of the surface of the electrolytic bath.
  • the produced metal fine particles can be easily collected. Moreover, it becomes difficult for impurities derived from the cathode base material to be mixed in the electrolytic bath and the generated metal fine particles.
  • a metal oxide powder can be used as a raw material, and it is possible to provide a method for producing metal fine particles in which impurities are hardly mixed in an electrolytic bath and generated metal fine particles. .
  • the reduction of the metal oxide powder is preferably performed while stirring the electrolytic bath.
  • the method for producing fine metal particles according to the present invention includes (a) a step of preparing a molten salt, (b) a step of suspending a metal oxide powder in the molten salt to generate an electrolytic bath, and (c) A) disposing an anode in the electrolytic bath; (d) disposing a cathode near the surface of the electrolytic bath outside the electrolytic bath; and (e) generating a discharge between the cathode and the electrolytic bath surface. And applying a voltage for reducing the metal oxide powder between the anode and the cathode and energizing.
  • a metal oxide powder is suspended in a molten salt to form an electrolytic bath, and a discharge is generated between the cathode and the surface of the electrolytic bath to reduce the voltage of the metal oxide powder between the anode and the cathode.
  • the metal oxide powder can be reduced by applying and applying current between the two.
  • the metal oxide When the metal oxide is in a powder form, the metal oxide is easily suspended and dispersed in the molten salt, and the reduction of the metal oxide powder easily proceeds uniformly.
  • the cathode in the vicinity of the electrolytic bath rather than immersing it in the electrolytic bath, impurities from the cathode base material are less likely to be mixed into the electrolytic bath and the generated metal fine particles.
  • the metal since the metal is not electrodeposited on the cathode, but is produced in the electrolytic bath as fine metal particles, the produced fine metal particles are easily recovered.
  • a metal oxide powder can be used as a raw material, and it is possible to provide a method for producing metal fine particles in which impurities are hardly mixed in an electrolytic bath and generated metal fine particles. .
  • the metal oxide as a raw material is preferably an oxide of silicon, titanium, tantalum, niobium, iron, cobalt, nickel, aluminum, or tungsten.
  • the content of the metal oxide powder in the molten salt is preferably 0.1 to 20 wt% with respect to the weight of the molten salt.
  • the content of the metal oxide relative to the weight of the molten salt is less than 0.1 wt%, the amount of the metal oxide supplied to the vicinity of the cathode decreases, and the reduction reaction may not proceed smoothly.
  • the content is larger than 20 wt%, the electrolyte bath is not suspended or dispersed in the electrolytic bath, but settles at the bottom of the electrolytic bath or stays on the surface of the electrolytic bath, and the viscosity of the electrolytic bath increases. In some cases, the electrolytic operation may be difficult. Therefore, when the content of the metal oxide powder is 0.1 to 20 wt% with respect to the weight of the molten salt, these difficulties can be avoided.
  • the metal oxide powder preferably has an average particle diameter of 0.5 nm to 100 ⁇ m.
  • the metal oxide powder can be uniformly suspended and dispersed in the electrolytic bath, the uniformity of the composition and particle diameter of the obtained metal fine particles can be improved.
  • the molten salt is LiF, NaF, KF, RbF, CsF, LiCl, NaCl, KCl, RbCl, CsCl, LiBr, NaBr, KBr, RbBr, CsBr, LiI, NaI. , KI, RbI or alkali metal halide CsI, MgF 2, CaF 2, SrF 2, BaF 2, MgCl 2, CaCl 2, SrCl 2, BaCl 2, MgBr 2, CaBr 2, SrBr 2, BaBr 2,, MgI 2, CaI 2, SrI 2 , or preferably contains at least one or more alkaline earth metal halides BaI 2.
  • the temperature of the electrolytic bath is preferably 300 ° C. to 1000 ° C.
  • the composition of the molten salt that can be used is greatly limited, and the solubility and diffusion rate of the oxide ions in the molten salt are lowered to lower the anode current density.
  • the anode structure In order to obtain, it is necessary to devise the anode structure, the electrolytic cell structure, and the like.
  • the operation is carried out at a higher temperature, the actual operational problems increase, for example, the device structural material used in the electrolytic cell is greatly limited. Therefore, by setting the temperature of the electrolytic bath to 300 ° C. to 1000 ° C., it is possible to produce metal fine particles while maintaining the degree of freedom of the composition of the molten salt used and the structural material.
  • the temperature of the electrolytic bath is more preferably 400 ° C. to 700 ° C.
  • a metal oxide powder as a raw material, and to provide a method for producing metal fine particles in which impurities are hardly mixed in an electrolytic bath and generated metal fine particles. can do.
  • an apparatus 1 for producing metal fine particles 112 for carrying out a method for producing metal fine particles 112 includes a container 10 that houses an electrolytic bath 100, an anode 21, a cathode 22, a power supply unit 23 to which the anode 21 and the cathode 22 are connected, an argon gas supply unit 30, and an argon atmosphere holding unit 40.
  • the electrolytic bath 100 includes a molten salt and a metal oxide powder 110.
  • the metal oxide powder 110 is suspended and dispersed in the electrolytic bath.
  • the metal fine particles 112 are generated in the electrolytic bath 100.
  • the metal oxide powder 110 suspended in the molten salt contained in the electrolytic bath 100 will be described.
  • the metal oxide powder 110 is not particularly limited as long as the metal oxide powder 110 is an oxide powder of a metal oxide or an alloy thereof that is electrochemically reduced in a molten salt to obtain a metal.
  • the metal oxide powder 110 is particularly preferably an oxide of silicon, titanium, tantalum, niobium, iron, cobalt, nickel, aluminum, or tungsten.
  • the purity of the metal oxide powder 110 is not particularly limited. In order to obtain the high-purity metal fine particles 112, it is preferable to use a metal oxide powder 110 having a higher purity.
  • the crystallinity of the metal oxide powder 110 is not particularly limited.
  • the metal oxide powder 110 may be single crystal or amorphous.
  • the amount of the metal oxide powder 110 suspended in the molten salt of the electrolytic bath 100 is not particularly limited as long as the reduction reaction of the metal oxide powder 110 proceeds.
  • the metal oxide powder 110 is preferably 0.1 to 20 wt% with respect to the weight of the molten salt. When the content of the metal oxide powder 110 with respect to the weight of the molten salt is less than 0.1 wt%, the amount of the metal oxide powder 110 supplied in the vicinity of the cathode 22 is reduced and the reduction reaction proceeds smoothly. May be difficult.
  • the metal oxide powder 110 with respect to the weight of the molten salt is larger than 20 wt%, the metal oxide powder 110 is not suspended in the electrolytic bath 100 but is precipitated at the bottom of the electrolytic bath 100 or The electrolytic bath 100 may become difficult, and the electrolytic bath 100 may be difficult to perform. Therefore, when the metal oxide powder 110 is 0.1 to 20 wt% with respect to the weight of the molten salt, these difficulties can be avoided. In addition, when performing electrolysis continuously, it is preferable not to add a necessary amount at a time, but to appropriately supply an appropriate amount according to the progress of electrolysis.
  • the size of the metal oxide powder 110 suspended in the molten salt of the electrolytic bath 100 needs to be appropriately adjusted according to the specific gravity of the metal oxide powder 110, but the average particle size is 0.5 nm to 100 ⁇ m. Preferably there is. By doing so, since the metal oxide powder can be uniformly suspended and dispersed in the electrolytic bath, the uniformity of the composition and particle diameter of the obtained metal fine particles 112 can be enhanced. Further, when the average particle size of the metal oxide powder 110 is large, there is a high possibility that the reduction reaction does not reach the inside of the powder, and it is easy to settle in the electrolytic bath. Turbidity / dispersion becomes difficult. On the other hand, when the average particle size is small, it is difficult to reliably add the powder to the atmosphere at the time of addition or to remain on the bath surface. is there.
  • the molten salt of the electrolytic bath 100 will be described.
  • the molten salt used include LiF, NaF, KF, RbF, CsF, LiCl, NaCl, KCl, RbCl, CsCl, LiBr, NaBr, KBr, RbBr, CsBr, LiI, NaI, KI, RbI, CsI and the like.
  • alkali metal halides MgF 2, CaF 2, SrF 2, BaF 2, MgCl 2, CaCl 2, SrCl 2, BaCl 2, MgBr 2, CaBr 2, SrBr 2, BaBr 2, MgI 2, CaI 2, SrI 2 And at least one of alkaline earth metal halides such as BaI 2 .
  • These compounds can be used individually or in combination of 2 or more types. The combination and mixing ratio are not limited, and may be set as appropriate according to the desired operating temperature.
  • a molten salt having a composition with a higher specific gravity is used in order to avoid rapid precipitation of the oxide powder in the electrolytic bath and difficulty in suspension. Is preferred.
  • the bath temperature of the electrolytic bath 100 may be appropriately adjusted according to the type of the target metal, the composition of the molten salt used, etc., but is preferably 300 to 1000 ° C., more preferably 400 to 700 ° C. .
  • the composition of the molten salt that can be used is greatly limited, and the solubility and diffusion rate of the oxide ions in the molten salt are lowered to lower the anode current density.
  • the operation is carried out at a higher temperature, the actual operational problems increase, for example, the device structural material used in the electrolytic cell is greatly limited.
  • the anode 21, the cathode 22, and the power supply unit 23 will be described.
  • the cathode (discharge cathode) 22 any cathode 22 that is usually used in plasma-induced electrolysis can be used, and tungsten can be exemplified.
  • the oxide ions 111 generated by the reduction of the metal oxide powder 110 are oxidized to generate oxygen gas. Therefore, the oxygen generating anode 21 usually used in molten salt electrolysis can be used, and conductive ceramics such as nickel ferrite and conductive diamond can be exemplified.
  • the concentration of the oxide ion 111 in the electrolytic bath 100 is low, such as immediately after the start of electrolysis, depending on the magnitude of the electrolysis current, for example, when a molten chloride such as LiCl—KCl is used as the molten salt, the anode 21 Chlorine is generated and the anode 21 may be worn out.
  • carbon electrodes such as graphite and glassy carbon are selectively used according to the reaction of the anode 21, or oxide ions 111 are supplied into the electrolytic bath 100 in advance by addition of lithium oxide, calcium oxide, etc. It is preferable to take measures such as making the anodic reaction oxygen generation.
  • the electrolytic bath preferably contains an alkali metal oxide or an alkaline earth metal oxide such as lithium oxide or calcium oxide.
  • oxide ions can be supplied into the electrolytic bath, the oxide ions are oxidized at the anode immediately after the start of electrolysis to generate oxygen gas.
  • an insoluble oxygen generating anode such as nickel ferrite from the initial stage of electrolysis.
  • the power source unit 23 is for applying a voltage between the anode 21 and the cathode 22 to generate a discharge between the cathode 22 and the surface of the electrolytic bath and to reduce the metal oxide powder 110. .
  • the argon gas supply unit 30 is for supplying argon gas into the electrolytic bath 100.
  • the electrolytic bath 100 is agitated by supplying argon gas into the electrolytic bath 100.
  • the argon gas supply unit 30 is an example of a stirring unit that stirs the electrolytic bath 100.
  • gas stirring by blowing an inert gas such as argon or nitrogen, mechanical stirring by a stirring blade, stirring by a high temperature stirring bar made of a magnet enclosed in glass or ceramics, MHD convection The agitation by can be exemplified.
  • the argon atmosphere holding unit 40 is for keeping the periphery of the electrolytic bath 100 and the cathode 22 in an argon atmosphere.
  • the argon atmosphere holding unit 40 may be formed of a box that covers the entire electrolytic bath 100 and the cathode 22.
  • the argon atmosphere holding unit 40 includes an argon gas discharge unit 41. The argon gas supplied into the argon atmosphere holding unit 40 by the argon gas supply unit 30 is discharged to the outside of the argon gas atmosphere holding unit 40 through the argon gas discharge unit 41.
  • step (a) a molten salt is prepared.
  • step (b) the electrolytic bath 100 is generated by suspending the metal oxide powder 110 as a raw material in the molten salt.
  • step (c) the anode 21 is disposed in the electrolytic bath 100
  • step (d) the cathode 22 is disposed in the vicinity of the electrolytic bath 100.
  • the cathode 22 is disposed in the vicinity of the surface of the electrolytic bath 100 above the surface of the electrolytic bath 100.
  • step (e) a discharge is generated between the cathode 22 and the electrolytic bath surface, and a voltage for reducing the metal oxide powder 110 is applied between the anode 21 and the cathode 22 and energized.
  • step (f) the electrolytic bath 100 is stirred. Note that the steps (a) to (f) may be performed in the order of the above (a) to (f), or may be performed in another order. A plurality of steps may be performed simultaneously.
  • the electrolytic bath 100 containing the molten salt in which the metal oxide powder 110 is suspended is stirred by the argon gas blown into the electrolytic bath 100 by the argon gas supply unit 30, so that the metal oxide powder 110 is directly below the cathode 22. Always supplied near the electrolytic bath surface. In the vicinity of the surface of the electrolytic bath immediately below the cathode 22, the metal oxide powder 110 is electrochemically reduced by the discharge electrons 120 supplied from the cathode 22 into the electrolytic bath 100, and oxide ions 111 and metal fine particles 112 are generated. To do. The oxide ions 111 are oxidized at the anode 21 to become oxygen gas 130.
  • the metal fine particles 112 generated in the electrolytic bath 100 are recovered together with the molten salt. Finally, the solidified salt is removed by washing with water, and the metal fine particles 112 can be obtained.
  • the method for producing the metal fine particles 112 generates a cathode discharge in the vicinity of the surface of the electrolytic bath 100 in which the metal oxide powder 110 is suspended and dispersed in the molten salt.
  • the oxide powder 110 is reduced.
  • the method for producing the metal fine particles 112 includes (a) a step of preparing a molten salt, (b) a step of suspending the metal oxide powder 110 in the molten salt to generate the electrolytic bath 100, and (c). Disposing the anode 21 in the electrolytic bath 100, (d) disposing the cathode 22 near the surface of the electrolytic bath 100 outside the electrolytic bath 100, and (e) between the cathode 22 and the electrolytic bath surface. And applying a voltage between the anode 21 and the cathode 22 to generate a discharge and reducing the metal oxide powder 110 to energize.
  • the metal oxide powder 110 is suspended in the molten salt to form the electrolytic bath 100, and a discharge is generated between the cathode 22 and the surface of the electrolytic bath.
  • the metal oxide powder 110 can be reduced by applying a voltage between the anode 21 and the cathode 22 to energize the metal oxide powder 110.
  • the metal oxide powder 110 is generally inexpensive and easily available as compared with the bulk metal or metal halide constituting the target metal fine particles 112. Further, since the metal oxide powder 110 may be suspended in the electrolytic bath 100, the composition of the molten salt to be used is compared with the case where the metal oxide powder 110 is chemically dissolved in the electrolytic bath 100. The restrictions imposed are relaxed. In addition, since the metal oxide powder 110 is in a powder form, the metal oxide powder 110 is easily suspended and dispersed in the electrolytic bath, and the reduction of the metal oxide powder 110 easily proceeds uniformly.
  • the metal oxide powder 110 is reduced by cathode discharge in the vicinity of the surface of the electrolytic bath 100. 22 impurities derived from the base material are less likely to be mixed into the electrolytic bath 100 or the metal fine particles 112. Further, since the metal is not electrodeposited on the cathode 22 but is generated in the electrolytic bath as metal fine particles, the produced metal fine particles can be easily collected.
  • a metal oxide powder can be used as a raw material, and it is possible to provide a method for producing metal fine particles in which impurities are hardly mixed in an electrolytic bath and generated metal fine particles. .
  • the reduction of the metal oxide powder 110 is performed while stirring the electrolytic bath 100, so that the reduction of the metal oxide powder 110 easily proceeds uniformly.
  • metal fine particles particularly nanoparticles, were produced by the method for producing metal fine particles of the present invention.
  • a molten LiCl—KCl eutectic composition salt 200 g was melted under an atmospheric pressure argon atmosphere and maintained at 450 ° C.
  • step (b) of suspending the metal oxide powder in the molten salt to form an electrolytic bath 3 g of silicon dioxide powder (SiO 2 , 325 mesh) is added, and the electrolytic bath is stirred by blowing argon gas. As a result, it was suspended and dispersed in the electrolytic bath.
  • step (c) of placing the anode in the electrolytic bath an anode made of glassy carbon was placed in the electrolytic bath.
  • a tungsten rod was disposed above the surface of the electrolytic bath as a cathode serving as a discharge electrode.
  • plasma induced cathode electrolysis electrolytic current 1A, 20,000C
  • the particles formed in the bath were collected together with the molten salt, and the cooled and solidified salt was removed by washing with water to obtain the produced particles.

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
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Abstract

Cette invention concerne un procédé de production de microparticules de métal dans lequel il est possible d'utiliser un oxyde métallique en tant que matière première et dans lequel les impuretés ne se mélangent pas facilement aux sels fondus et aux microparticules de métal générées. Un procédé de production de microparticules de métal (112) est utilisé pour réduire des poudres d'oxyde métallique (110) dans un bain électrolytique (100) par génération d'une décharge cathodique à proximité de la surface du bain électrolytique (100) dans lequel les poudres d'oxyde métallique (110) sont suspendues dans des sels fondus.
PCT/JP2011/073877 2010-11-02 2011-10-18 Procédé de production de microparticules de métal WO2012060208A1 (fr)

Priority Applications (2)

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JP2012541802A JPWO2012060208A1 (ja) 2010-11-02 2011-10-18 金属微粒子の製造方法
US13/882,816 US9562296B2 (en) 2010-11-02 2011-10-18 Production method for silicon nanoparticles

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JP2010-246040 2010-11-02
JP2010246040 2010-11-02

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KR101628575B1 (ko) * 2014-12-24 2016-06-08 현대자동차주식회사 이온성 액체 전기 도금 기법을 이용한 염료감응형 태양전지용 고내식성 탄탈룸-은 복합 전극 제조방법
KR101840388B1 (ko) 2014-12-12 2018-03-20 한국기초과학지원연구원 금속입자의 산화를 억제하는 플라즈마 전기화학 장치
CN109317691A (zh) * 2018-10-15 2019-02-12 中南大学 一种高分散杆状紫钨的制备方法
WO2023058775A1 (fr) * 2021-10-08 2023-04-13 Ｓｅｃカーボン株式会社 Procédé destiné à la production de particules de graphite

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